WO1993017140A1 - Cemented carbide with binder phase enriched surface zone - Google Patents
Cemented carbide with binder phase enriched surface zone Download PDFInfo
- Publication number
- WO1993017140A1 WO1993017140A1 PCT/SE1993/000140 SE9300140W WO9317140A1 WO 1993017140 A1 WO1993017140 A1 WO 1993017140A1 SE 9300140 W SE9300140 W SE 9300140W WO 9317140 A1 WO9317140 A1 WO 9317140A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder phase
- content
- cemented carbide
- insert
- zone
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/057—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of phases other than hard compounds by solid state reaction sintering, e.g. metal phase formed by reduction reaction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
Definitions
- the present invention relates to coated cemented carbide inserts with a binder phase enriched surface zone and a process for the making of the same. More par ⁇ ticularly the present invention relates to coated in ⁇ serts in which the cemented carbide has been modified so that unique technological properties have been obtained at a given chemical composition and grain size regarding the balance between very good toughness behaviour in combination with high resistance against plastic defor ⁇ mation.
- Coated cemented carbide inserts with binder phase enriched surface zone are today used to a great extent for machining of steel and stainless materials. Thanks to the binder phase enriched surface zone an extension of the application area for the cutting tool material has been obtained.
- Methods or processes to make cemented carbide con ⁇ taining WC, cubic phase (gamma-phase) and binder phase with binder phase enriched surface zones are within the technique referred to as gradient sintering and are known through a number patents and patent applications . According to, e.g., U.S. Patents 4,277,283 and 4,610,931 nitrogen containing additions are used and sintering ta ⁇ kes place in vacuum whereas according to U.S.
- Patent 4,548,786 the nitrogen is added in gas phase.
- a binder phase enriched surface zone essen- tially depleted of cubic phase is obtained.
- U.S. Patent 4,830,930 describes a binder phase enrichment obtained through decarburization after the sintering whereby a binder phase enrichment is obtained which also contains cubic phase.
- nitrogen gas is used in connection with the sintering in order to eliminate a process step and to improve the adhesion of a subse ⁇ quently deposited oxide coating. From fracture mechanics point of view, an enrichment of binder metal in a surface zone means that the ability • of the cemented carbide to absorb deformation and stop growing cracks increases.
- a material is ob ⁇ tained with improved ability to withstand fracture by allowing greater deformations or by preventing cracks from growing, compared to a material with mainly the same composition but homogeneous microstruc ure.
- the cutting material thus, obtains a tougher behaviour.
- gradient sintering according to the known technique of vacuum sintering of nitrogen containing ce ⁇ mented carbide, the nitrogen is usually added by adding of a small amount of nitrogen containing raw materials. Due to the fact that the nitrogen activity in the fur ⁇ nace atmosphere at the sintering is below the average nitrogen activity in the cubic phase, the nitrogen con ⁇ taining cubic phase will give off nitrogen through the liquid binder phase to the furnace atmosphere.
- a characteristic distribution of Co, Ti and W as a ' function of the distance from the surface of a cemented carbide with binder phase enrichment obtained through the above mentioned process appears, e.g., from fig 1 in U.S. 4,830,930. Outermost, there is a surface zone enriched in binder phase and completely or partly de ⁇ pleted of cubic phase. Inside this surface zone there is an area with an enrichment of the metallic element (s) present in the cubic phase, in particular Ti, Ta and Nb and where the binder phase content is considerably lower than the average content of binder phase in the interior of the cemented carbide body.
- the decrease in binder phase content for cemented carbide with about 6 weight-% cobalt and 9 weight-% cubic phase can be up to about 2 weight-%, i.e., a relative decrease of the order of 30 %. Cracks grow easily in this zone, which has a decisive influence on the fracture frequency during machining.
- Figure 1 shows the distribution of Co and Ti as a function of the distance from the surface of a binder phase enriched cemented carbide according to the inven ⁇ tion.
- Figure 2 shows the distribution of Co and Ti as a function of the distance from the surface of a binder phase enriched cemented carbide according to known technique.
- Figure 3 is a light optical micrograph in 120OX of the surface zone of a cemented carbide according to the invention in which A is surface zone enriched in binder phase and essentially free from cubic phase and B is the upper part of the zone according to the invention.
- the present invention relates to a process performed after gradient sintering comprising sintering in vacuum or inert atmosphere of a nitrogen containing cemented carbide either as a separate process step or integrated into the gradient sintering process.
- the process com ⁇ prises supplying nitrogen gas to the sintering furnace at a pressure of 40-400 mbar, preferably 150-350 mbar, at a temperature between 1280 and 1430°C, preferably between 1320 and 1400°C.
- a suitable time for the nitro ⁇ gen gas treatment is 5-100 min, preferably 10-50 min.
- the nitrogen gas is maintained until a temperature where the binder phase solidifies at about 1275-1300°C.
- the main part of the effect is, however, achieved even if the binder phase solidifies in vacuum or in inert at ⁇ mosphere. It is particularly suitable to introduce a holding time for the nitrogen gas treatment of 5-50 min at a temperature of 1350-1380°C and a pressure of 200- 350 mbar for cemented carbides with a content of cubic phase of 6-10 weight-% expressed according to below or at 1280-1320 at a pressure of 50-150 mbar at a content of cubic phase of 8-15 weight-%.
- the process according to the present invention is particularly intended to be applied to binder phase en- riched cemented carbide made by sintering in vacuum or inert atmosphere at very low pressure of nitrogen of ni ⁇ trogen containing material. It is effective on cemented carbide containing titanium, tantalum, niobium, tung ⁇ sten, vanadium and/or molybdenum and a binder phase ba- sed on Co and/or Ni.
- An optimal combination of toughness and resistance against plastic deformation is obtained when the amount of cubic phase expressed as the total content of metallic elements forming cubic carbides i.e.
- Ti, Ta, Nb etc is between 6 and 15 weight-%, preferably between 7-10 weight-% at a titanium content of 0.4-10 weight-%, preferably 1-4 weight-% for turning and 2-10 weight-% for milling and when the binder phase content is between 3.5 and 12 weight-% for turning, preferably between 5 and 7.5 weight-% and for milling, preferably between 6 and 12 weight-%.
- the carbon content can be below carbon saturation up to a content corresponding to maximum C08, preferably C02-C08.
- a cemented carbide with improved toughness and resis ⁇ tance against plastic deformation containing WC and cu ⁇ bic phases of carbonitride and/or carbide, preferably containing Ti in a binder phase based on Co and/or Ni with a, preferably ⁇ 50 ⁇ thick binder phase enriched surface zone is obtained.
- binder phase enriched there is a ⁇ 300 ⁇ m, preferably ⁇ 200 ⁇ m thick zone with a binder phase content of 0.85-1, prefe ⁇ rably 0.9-1, most preferably 0.92-1 of the content in the inner portion of the cemented carbide and where the content of cubic phase is essentially constant and equal to the content in the inner portion of the cemented car ⁇ bide.
- the binder phase enriched zone is essentially free from cubic phase i.e. it contains WC and binder phase except for the very surface where the share of cubic phase is ⁇ 50 volume-%.
- the binder phase content in the binder phase enriched zone has within a distance from the surface of 10-30 ⁇ a maximum of >1.1, preferably 1.25-2 of the content in the inner portion of the ce ⁇ mented carbide.
- Cemented carbide according to the invention is sui ⁇ tably coated with in itself known thin wear resistant coating with CVD- or PVD-technique.
- a layer of carbide, nitride or carbonitride of, preferably tita ⁇ nium is applied as the innermost layer.
- the cemented carbide Prior to the coating the cemented carbide is cleaned, e.g., by blas ⁇ ting so that possible graphite and cubic phase are es ⁇ sentially removed.
- the present invention improves the properties of the cemented carbide.
- no zone is obtained in the material where propagation of cracks is favourable.
- a cemented carbide is obtained with consi ⁇ derably tougher behaviour than possible using known technique.
- a treatment according to the in- vention was made as 30 min at 1375°C with an atmosphere of 300 mbar N2 and thereafter continued cooling in N2 down to 1200°C where a gas change to Ar was made.
- the structure in the surface of the cutting insert consisted then of a 25 ⁇ m thick binder phase enriched zone essentially free from cubic phase and below that a zone slightly depleted of binder phase, 0.92-1 of the content in the inner portion of the insert and without essential enrichment of cubic phase, fig 1.
- Example 2 (reference example to Example 1)
- Example 2 From the same powder as in Example 1 inserts were pressed of the same type. These inserts were sintered according to the standard part of the sintering in Exam ⁇ ple 1, i.e., with a protective gas of Ar during the hol ⁇ ding time at 1450°C. The cooling was under a protective gas of Ar.
- the structure in the surface consisted of a 25 ⁇ m thick binder phase enriched zone essentially free from cubic phase. Below that zone, a 100-150 ⁇ m thick zone considerably depleted of binder phase, with a minimum of about 70 % of the nominal content in the inner portion of the insert and enriched of cubic phase was found as shown fig 2.
- the inner portion of the inserts showed C- porosity, C04. This is a typical structure for gradient sintered cemented carbide according to known technique.
- the inserts were edgerounded and coated according to known technique.
- Example 3 Example 3
- Example 6 (reference example to Example 5)
- the inserts were edgerounded and coated according Example 5.
- Example 7 With the milling inserts from Examples 5 and 6, a milling operation in a quenched and tempered steel SS 2541 was performed as a facemilling over a workpiece 50 mm thick. The milling was performed as one tooth milling with a milling body with a diameter of 125 mm. The il- ling body was positioned such that its centre was above the exit side of the workpiece. The following cutting data were used:
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Powder Metallurgy (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Carbon And Carbon Compounds (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Ceramic Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002130544A CA2130544C (en) | 1992-02-21 | 1993-02-19 | Cemented carbide with binder phase enriched surface zone |
JP51474993A JP3999261B2 (en) | 1992-02-21 | 1993-02-19 | Super hard alloy carbide with binder phase surface area |
KR1019940702730A KR100271068B1 (en) | 1992-02-21 | 1993-02-19 | Cemented carbide with binder phase enriched surface zone |
DE69334012T DE69334012T2 (en) | 1992-02-21 | 1993-02-19 | CEMENTED CARBIDE WITH BINDER PHASE OF ENRICHED SURFACE ZONE |
EP93905706A EP0627016B1 (en) | 1992-02-21 | 1993-02-19 | Cemented carbide with binder phase enriched surface zone |
RU94040362/02A RU2106932C1 (en) | 1992-02-21 | 1993-02-19 | Cutting plate from hard alloy and cutting plate manufacture method |
BR9305926A BR9305926A (en) | 1992-02-21 | 1993-02-19 | Cemented carbide with surface area enriched with binder phase |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9200530A SE9200530D0 (en) | 1992-02-21 | 1992-02-21 | HARD METAL WITH BINDING PHASE ENRICHED SURFACE |
SE9200530-5 | 1992-02-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993017140A1 true WO1993017140A1 (en) | 1993-09-02 |
Family
ID=20385401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE1993/000140 WO1993017140A1 (en) | 1992-02-21 | 1993-02-19 | Cemented carbide with binder phase enriched surface zone |
Country Status (13)
Country | Link |
---|---|
US (2) | US5549980A (en) |
EP (1) | EP0627016B1 (en) |
JP (1) | JP3999261B2 (en) |
KR (1) | KR100271068B1 (en) |
CN (1) | CN1038731C (en) |
AT (1) | ATE323786T1 (en) |
BR (1) | BR9305926A (en) |
CA (1) | CA2130544C (en) |
DE (1) | DE69334012T2 (en) |
IL (1) | IL104747A (en) |
RU (1) | RU2106932C1 (en) |
SE (1) | SE9200530D0 (en) |
WO (1) | WO1993017140A1 (en) |
Cited By (10)
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WO1998016665A1 (en) * | 1996-10-11 | 1998-04-23 | Sandvik Ab (Publ) | Method of making cemented carbide with binder phase enriched surface zone |
DE19907749A1 (en) * | 1999-02-23 | 2000-08-24 | Kennametal Inc | Sintered hard metal body useful as cutter insert or throwaway cutter tip has concentration gradient of stress-induced phase transformation-free face-centered cubic cobalt-nickel-iron binder |
EP1043415A2 (en) * | 1999-04-08 | 2000-10-11 | Sandvik Aktiebolag | Cemented carbide insert |
WO2001073146A2 (en) * | 2000-03-24 | 2001-10-04 | Kennametal Inc. | Cemented carbide tool and method of making |
WO2002050337A1 (en) * | 2000-12-19 | 2002-06-27 | Sandvik Ab | Coated cemented carbide cutting tool insert |
US6638474B2 (en) | 2000-03-24 | 2003-10-28 | Kennametal Inc. | method of making cemented carbide tool |
EP0682580B2 (en) † | 1993-02-05 | 2005-06-01 | Sandvik Aktiebolag | Cemented carbide with binder phase enriched surface zone and enhanced edge toughness behaviour |
EP1715082A1 (en) * | 2005-04-20 | 2006-10-25 | Sandvik Intellectual Property AB | Coated cemented carbide with binder phase enriched surface zone |
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SE514177C2 (en) * | 1995-07-14 | 2001-01-15 | Sandvik Ab | Coated cemented carbide inserts for intermittent machining in low alloy steel |
EP0874919B1 (en) * | 1995-11-30 | 2002-02-13 | Sandvik Aktiebolag | Coated turning insert and method of making it |
SE9504304D0 (en) * | 1995-11-30 | 1995-11-30 | Sandvik Ab | Coated milling insert |
US5955186A (en) * | 1996-10-15 | 1999-09-21 | Kennametal Inc. | Coated cutting insert with A C porosity substrate having non-stratified surface binder enrichment |
EP1095168B1 (en) * | 1998-07-08 | 2002-07-24 | Widia GmbH | Hard metal or ceramet body and method for producing the same |
SE9802488D0 (en) | 1998-07-09 | 1998-07-09 | Sandvik Ab | Coated grooving or parting insert |
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SE516017C2 (en) | 1999-02-05 | 2001-11-12 | Sandvik Ab | Cemented carbide inserts coated with durable coating |
SE519828C2 (en) | 1999-04-08 | 2003-04-15 | Sandvik Ab | Cut off a cemented carbide body with a binder phase enriched surface zone and a coating and method of making it |
US6217992B1 (en) | 1999-05-21 | 2001-04-17 | Kennametal Pc Inc. | Coated cutting insert with a C porosity substrate having non-stratified surface binder enrichment |
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-
1992
- 1992-02-21 SE SE9200530A patent/SE9200530D0/en unknown
-
1993
- 1993-02-16 IL IL10474793A patent/IL104747A/en not_active IP Right Cessation
- 1993-02-19 RU RU94040362/02A patent/RU2106932C1/en active
- 1993-02-19 JP JP51474993A patent/JP3999261B2/en not_active Expired - Lifetime
- 1993-02-19 CA CA002130544A patent/CA2130544C/en not_active Expired - Lifetime
- 1993-02-19 EP EP93905706A patent/EP0627016B1/en not_active Expired - Lifetime
- 1993-02-19 AT AT93905706T patent/ATE323786T1/en active
- 1993-02-19 KR KR1019940702730A patent/KR100271068B1/en not_active IP Right Cessation
- 1993-02-19 WO PCT/SE1993/000140 patent/WO1993017140A1/en active IP Right Grant
- 1993-02-19 DE DE69334012T patent/DE69334012T2/en not_active Expired - Lifetime
- 1993-02-19 BR BR9305926A patent/BR9305926A/en not_active IP Right Cessation
- 1993-02-20 CN CN93102964A patent/CN1038731C/en not_active Expired - Lifetime
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1994
- 1994-06-10 US US08/258,598 patent/US5549980A/en not_active Expired - Lifetime
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1996
- 1996-03-15 US US08/616,312 patent/US5761593A/en not_active Expired - Lifetime
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Cited By (19)
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EP0682580B2 (en) † | 1993-02-05 | 2005-06-01 | Sandvik Aktiebolag | Cemented carbide with binder phase enriched surface zone and enhanced edge toughness behaviour |
WO1998016665A1 (en) * | 1996-10-11 | 1998-04-23 | Sandvik Ab (Publ) | Method of making cemented carbide with binder phase enriched surface zone |
DE19907749A1 (en) * | 1999-02-23 | 2000-08-24 | Kennametal Inc | Sintered hard metal body useful as cutter insert or throwaway cutter tip has concentration gradient of stress-induced phase transformation-free face-centered cubic cobalt-nickel-iron binder |
US6655882B2 (en) | 1999-02-23 | 2003-12-02 | Kennametal Inc. | Twist drill having a sintered cemented carbide body, and like tools, and use thereof |
EP1043415A3 (en) * | 1999-04-08 | 2002-08-14 | Sandvik Aktiebolag | Cemented carbide insert |
EP1043415A2 (en) * | 1999-04-08 | 2000-10-11 | Sandvik Aktiebolag | Cemented carbide insert |
WO2001073146A3 (en) * | 2000-03-24 | 2002-02-21 | Kennametal Inc | Cemented carbide tool and method of making |
US6638474B2 (en) | 2000-03-24 | 2003-10-28 | Kennametal Inc. | method of making cemented carbide tool |
WO2001073146A2 (en) * | 2000-03-24 | 2001-10-04 | Kennametal Inc. | Cemented carbide tool and method of making |
AU2001245893B2 (en) * | 2000-03-24 | 2005-09-29 | Kennametal Inc. | Cemented carbide tool and method of making |
US6998173B2 (en) | 2000-03-24 | 2006-02-14 | Kennametal Inc. | Cemented carbide tool and method of making |
KR100835694B1 (en) * | 2000-03-24 | 2008-06-05 | 케나메탈 아이엔씨. | Cemented carbide tool and method of making |
WO2002050337A1 (en) * | 2000-12-19 | 2002-06-27 | Sandvik Ab | Coated cemented carbide cutting tool insert |
US6692822B2 (en) | 2000-12-19 | 2004-02-17 | Sandvik Aktiebolag | Coated cemented carbide cutting tool insert |
EP1715082A1 (en) * | 2005-04-20 | 2006-10-25 | Sandvik Intellectual Property AB | Coated cemented carbide with binder phase enriched surface zone |
US7939013B2 (en) | 2005-04-20 | 2011-05-10 | Sandvik Intellectual Property Ab | Coated cemented carbide with binder phase enriched surface zone |
DE112015005009B4 (en) | 2014-12-24 | 2022-09-01 | Korloy Inc. | cutting tool |
CN110408829A (en) * | 2019-08-26 | 2019-11-05 | 广东技术师范大学 | A kind of cutter and preparation method thereof that gradient laminated coating is combined with gradient hard alloy |
CN110408829B (en) * | 2019-08-26 | 2021-07-16 | 广东技术师范大学 | Cutter combining gradient multilayer coating with gradient hard alloy and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
ATE323786T1 (en) | 2006-05-15 |
CN1038731C (en) | 1998-06-17 |
SE9200530D0 (en) | 1992-02-21 |
CN1079179A (en) | 1993-12-08 |
US5549980A (en) | 1996-08-27 |
RU94040362A (en) | 1996-06-27 |
JPH07503996A (en) | 1995-04-27 |
IL104747A0 (en) | 1993-06-10 |
KR100271068B1 (en) | 2000-11-01 |
DE69334012T2 (en) | 2006-11-23 |
CA2130544C (en) | 2005-04-26 |
DE69334012D1 (en) | 2006-05-24 |
JP3999261B2 (en) | 2007-10-31 |
CA2130544A1 (en) | 1993-09-02 |
IL104747A (en) | 1996-10-31 |
KR950700433A (en) | 1995-01-16 |
BR9305926A (en) | 1997-08-26 |
US5761593A (en) | 1998-06-02 |
EP0627016A1 (en) | 1994-12-07 |
EP0627016B1 (en) | 2006-04-19 |
RU2106932C1 (en) | 1998-03-20 |
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